Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners

ABSTRACT

Compositions useful in the aqueous cold-bleaching of textiles comprising (1) from 3 to 100 percent by weight of a bleaching component comprising (a) from 95 to 99.99 percent by weight of a mixture of (i) a percompound yielding H2O2 in aqueous solution and (ii) an activator for active oxygen selected from the group consisting of N-acyl and O-acyl compounds having 2 to 9 carbon atoms in the acyl, said activator having an activating action of at least 3 in the Per-Acid Formation Test, said percompound and said activator being present in such ratio that from 0.01 to 4 mols of said activator are present for each gram-atom of active oxygen in said percompound, and (b) from 0.01 to 5 percent by weight of at least one optical brightener selected from the group consisting of 4,4&#39;&#39;-bis-(azolyl)-stilbene-2,2&#39;&#39;-disulfonic acids, stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives, 2benzoxazolyl-4,5-naphthothiophene compounds, diphenyl-distyryl compounds and water-soluble acid addition salts thereof, and (2) from 0 to 97 percent of other customary ingredients of bleaching agents or washing agents having a bleaching effect.

United States Patent [191 Fries et a].

COMPOSITIONS USEFUL IN THE AQUEOUS COLD-BLEACHING OF TEXTILES INCLUDINGOPTICAL BRIGHTENERS [75] Inventors: Walter Fries, Erkrath-Unterbach;

Helmut Bloching, Monheim-Baumberg; Hilden Rhld, Monheim-Baumberg; DieterJung, Monheim-Baumberg, all of Germany [73] Assignee: I'lenkel & CieGmbH,

Dusseldorf-Holthausen, Germany [22] Filed: Sept. 27, 1971 2! Appl. N03184,213

[30] Foreign Application Priority Data Dec. 10, 1970 Germany 2060762July 12, 1971 Germany 2134691 [52] US. Cl 252/99, 8/1 1 l, 252/89,252/95, 252/102, 260/248 R [51] Int. Cl Clld 7/54 [58] Field of Search252/99, 95, 102, 252/89; 260/248 R [56] References Cited UNITED STATESPATENTS 3,637,339 l/l972 Gray 252/95 X 3,663,444 5/1972 SchmadeL...252/99 3,630,921 12/1971 Disch et a1. 252/95 3,655,569 4/1972 Hellstenet al 252/99 3,650,962 3/1972 Werdehausen et al. 252/102 3,284,462 1H1966 Liechti et a1 252/99 X FOREIGN PATENTS OR APPLICATIONS 1.059.601l/1958 Germany 252/102 Primary Examiner-Mayer Weinblatt Attorney-Hammond& Littell [5 7] ABSTRACT Compositions useful in the aqueouscold-bleaching of textiles comprising (1) from 3 to 100 percent byweight of a bleaching component comprising (a) from 95 to 99.99 percentby weight of a mixture of (i) a percompound yielding H O, in aqueoussolution and (ii) wmmflqy lk flfl qwnILQJD. the gmunmee afii tin m flNra xLane. gaexlesq ppunds having 2 to 9 carbon atoms in the acyl, saidactivator having an activating action of at least 3 in the Per- AcidFormation Test, said percompound and said activator being present insuch ratio that from 0.01 to 4 mols of said activator are present foreach gram-atom of active oxygen in said percompound, and (b) from 0.01to 5 percent by weight of at least one optical brightener selected fromthe group consisting of 4,4- bis-(azolyl)-stilbene-2,2f-disulfonicacids, stilbylnaphthotriazoles, bis-(benzoxazolyl)-derivatives, 2-benzoxazo1yl-4,5-naphthothiophene compounds, diphenyl-distyryl compoundsand water-soluble acid addition salts thereof, and (2) from 0 to 97percent of other customary ingredients of bleaching agents or washingagents having a bleaching effect.

8 Claims, No Drawings COMPOSITIONS USEFUL IN THE AQUEOUSCOLD-BLEACI'IING OF TEXTILES INCLUDING OPTICAL BRIGHTENERS THE PRIOR ARTIt is known to use aqueous solutions of hydrogen peroxide or ofpercompounds, yielding hydrogen peroxide in water, as oxidation andbleaching baths, particularly for fibrous substances and preferably fortextiles. These bleaching baths may also be solutions of bleachingwashing auxiliaries or washing agents. In such aqueous solutions theactive oxygen is effective generally only at temperatures of from 80C to100C.

It has also been proposed to use organic compounds that belong tocertain types of N-acyl or O-acyl com pounds, in such treatment baths asactivators for the percompounds. These activators transform the hydrogenperoxide present in the washing liquor into an organic peracid. By theprocess, the active oxygen is liberated at substantially lowertemperatures of, for instance, 20 to 70C, preferably 30 to 60C, in ableaching active state. The compositions intended for the preparation ofsuch treatment baths for textiles may contain optical brighteners.

Unfortunately, however, it was found that the bleaching baths containingN-acyl or O-acyl activators had undesirable side effects when utilizedin the presence of copper such as is present in most washing equipmentand, in addition, these bleaching baths containing N- acyl or O-acylactivators had an adverse effect on many optical brighteners alsopresent in the treatment bath or on the treated textiles.

OBJECTS OF THE INVENTION ing 2 to 9 carbon atoms in the acyl, saidactivator having an activating action of at least 3 in the Per-AcidFormation Test, said percompound and said activator being present insuch ratio that from 0.01 to 4 mols of said activator are present foreach gram-atom of active oxygen in said percompound, and (b) from 0.01to 5 percent by weight of at least one optical brightener selected fromthe group consisting of 4,4'-bis-(azolyl)- sti1bene-2,2-disulfonicacids, stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives,2-benzoxazolyl-4,5- naphthothiophene, diphenyldistyryl compounds andwater-soluble acid addition salts thereof, and (2) from 0.1 to 97percent by weight of at least one compound selected from the groupconsisting of (a) corrosion inhibitors selected from the groupconsisting of triazoles and tetrazoles, (b) water-soluble salts of aphosphorus acid ester selected from the group consisting of partialesters of fatty alcohols having from 10 to 22 carbon atoms and theirethoxylates and propoxylates having from 1 to 10 alkoxy units, withorthophosphoric acid, pyrophosphoric acid and polyphosphoric acids, (c)organic sequestering agents for heavy metal ions, (d) alkali metalalkaline-reacting inorganic builder salts, (e) stabiizers for saidpercompounds, (f) tensides selected from the group consisting of anionicsurface-active compounds, non-ionic surface-active compounds andamphoteric surface-active compounds, (g) watersoluble organic buildersalts, (h) antimicrobial agents, (i) soil suspension agents, (j)enzymes, (k) foam stabilizers, (l) non-surface-active foam inhibitors,(m) textile softeners, and (n) water.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention relates toactivator-containing compositions for the preparation of cold-bleachingliquors,

particularly of cold-bleaching active washing liquors.

sentially of (a) from 95 to 99.99 percent by weight of a mixture of (i)a percompound yielding H,O, in aqueous solution and (ii) an activatorfor active oxygen selected from the group consisting of N-acyl andO-acyl compounds having 2 to 9 carbon atoms in the acyl, said activatorhaving an activating action of at least 3 in the Per-Acid Formationtest, said percompound and said activator being present in such ratiothat from 0.01 to 4 mols of said activator are present for eachgram-atom of active oxygen in said percompound, and (b) from 0.01 to 5percent by weight of at least one optical brightener selected from thegroup consisting of 4,4- bis-(azolyl)-stilbene-2,2-disulfonic acids,stilbylnaphthotriazoles, bis-(benzoxazolyl)-derivatives, 2-benzoxazolyl-4,5-naphthothiophene, diphenyldistyryl compounds andwater-soluble acid addition salts thereof.

A further object of the invention is the development of a bleaching andoptical brightening composition useful in an aqueous cold-bleachingtreatment consisting essentially of 1) from 3 to 99.9 percent by weightof a bleaching component consisting essentially of (a) from 95 to 99.99percent by weight of a mixture of (i) a percompound yielding 11,0, inaqueous solution and (ii) an activator for active oxygen selected fromthe group consisting of N-acyl and O-acyl compounds hav- These agentsare characterized in that they contain:

3 to 100 percent, preferably 5 to percent, by weight of a bleachingcomponent, consisting of: a. 99.99 to percent, preferably 99.98 to 97.5percent, by weight of a percompound, yielding H,O, in aqueous solution,as well as an N-acyl or O-acyl compound, serving as activator forI-I,O,, that possesses an activations value determined by the Per- AcidFormation Test, for the percompound of at least 3, preferably of atleast 4.5, whereby the percompound and the activator are present in suchamounts, that at least 0.01 and at most 4, preferably at least 0.05 andat most 2, mols of activator are present per gram atom of active oxygenin said percompound. b. 0.01 to 5 percent, preferably 0.02 to 2.5percent, by weight of at least one optical brightener of the followingtypes: 4,4'-bis-(azolyl)-stilbene-2,2-disulfonic acids,stilbyl-naphthotriazoles,

bis-( benzoxazolyl)-derivatives,

diphenyldistyryl compounds, and/or 2-benzoxazolyl-4,5-naphthothiophene,whereby the named optical brighteners, insofar as they are acids,particularly sulfonic acids, are also present in the form of theirsalts.

97 to 0, preferably 95 to 10 percent by weight of other customaryingredients of bleaching agents or of bleaching washing agents.

The brighteners named under (b) may be utilized singularly or incombination.

Insofar as the optical brighteners. to be used according to theinvention, contain sulfonic acid or carboxylic acid residues, they arepreferably utilized in the form of their water-soluble alkali metalsalts, ammonium salts or salts of alkylamines and alkylolamines with 1to 6 carbon atoms in the molecule.

For reasons of simplification in the following, by activators," theabove-mentioned N-acyl or O-acyl compounds with the activation valuegiven there are understood.

The products of the invention may be utilized for the bleaching orbleaching laundering of many different fibers of natural or syntheticorigin. Cotton, regenerated cellulose or linen and particularly the easycare" textiles that consist of highly processed cotton or of syntheticfibers, such as polyamide, polyester, polyacrylonitrile, polyurethane,polyvinyl chloride or polyvinylidene chloride fibers or mixtures, may bebleached by the products of the invention. The textiles designated aseasy care" or no iron" include also such synthetic fibers-cotton mixedfabrics that may be specially finished.

The products of the invention are particularly suitable for thebleaching and the bleaching laundering of these easy care" textiles,since already at temperatures of 20to 70C, preferably 30 to 60C, on thebasis of the bleaching activation, a degree of whiteness is attainedsuch as can only be attained at temperatures of 70 to 100C, preferably80 to 95C in the absence of activators. The high degree of whiteness,attained with active oxygen and activators at lower temperatures, isabove all advantageous for the effect of the optical brighteners.

It has been found that the effect of conventional optical brighteners isoften impaired in the presence of the "activators." This impairment ismore strongly observed in the presence of heavy metals, such as copperin the washing liquor. These copper ions may be naturally present in thewater or may come from the cooper heating bars of the washing machine.These disadvantages and their cause were not previously known. It is,therefore, a particular merit of the invention to have found that theeffect of the above-named optical brighteners is not reduced by thepresence of activators."

Although the effect of the optical brighteners, to be utilized accordingto the invention, is not impaired or if impaired only in a substantiallyreduced extent than it is the case with other optical brighteners, itis, however, recommended to add to the products of the invention thebelow described phosphoric acid esters and/or corrosion inhibitors,whose amount may account for up to 25 percent by weight of thecomposition, as well as up to 10 percent by weight, preferably 0.1 to 7percent, by weight of organic sequestering agents for such ions. Thecompositions of the invention may contain as corrosion inhibitors thefollowing substances in the amounts stated:

to percent, preferably 0.1 to 2 percent, by weight of corrosioninhibitors of the triazole and/or tetrazole types, that contain a =NMegroup or =NOMe group, in which Me is a metal or a hydrogen atomreplaceable by a metal,

0 to 20 percent, preferably 1 to 10 percent, by weight of water-solublesalts of partial esters of fatty alcohols with 10 to 22, preferably 16to 18, carbon atoms of their ethoxylation and/or propoxylation products,containing 1 to 10, preferably 2 to 6, glycol ether groups in themolecule with ortho-, pyroor polyphosphoric acid (hereinafter calledphosphoric acid esters"). During the bleaching process the acyl radicalsof the activators" are liberated as carboxylic acids. it is recommended,therefore, to add to the agents, according to the invention, so much ofalkali metal salts of weak acids, that at least a fourth of thecarboxylic acids formed are bound as salts. Such salts are, forinstance, the alkali metal carbonates, alkali metal silicates and alkalimetal borates. Therefore, the formulation of the products of theinvention is advantageously in the following range: 5 to percent,preferably 10 to 70 percent, by

weight of the above described bleaching component, consisting ofpercompound, activator and brightener, to 25 percent, preferably 0.1 to20 percent, by weight of the above-described corrosion inhibitors,phosphoric acid esters and/or sequestering agents for heavy metals,particularly copper,

to 10 percent, preferably 89.9 to 10 percent, by weight of neutral, butpreferably alkaline-reacting builder salts customary in washing agentsor washing auxiliaries as well as, optionally, tensides, where suchamounts of alkali metal salts of weak acids are present, that the acylgroups contained in the activators on liberation are bound, at least toone fourth the total amount in the form of salts.

Bleaching textile treating agents, composed according to the aboveformulation may be marketed as special products for the textile industryor for commercial laundries or as soaking, prewash and washing agents,preferably usable in the home.

The special products for commercial use contain mostly more than 50percent by weight of the bleaching component of the invention, thisamount being based on the pure activator, the pure percompound and thepure brightener without further additives. Of course, such products mayalso be used at home for special purposes, for instance, as soaking orwashing agents with increased bleaching effect, that may be of interestas cold-washing agent, or as bleaching rinsing agent for the washedlaundry.

The products, to be used as soaking, prewash and washing agents for homeuse, contain mostly lesser amounts of percompounds, activators andoptical brighteners. These are present mostly in amounts of from 5 to 50percent preferably of from 10 to 35 percent by weight. In addition,these agents contain as further essential ingredients alkaline-reacting,nonsequestering builder salts as well as tensides. The above-describedphosphoric acid esters are at the same time tensides and may, for thisreason, be contained in larger amounts than given in the aboveformulation. The same goes accordingly for the sequestering agents forcopper. For this reason, in the following formulation for soaking,prewash and washing agents, the phosphoric acid esters are assigned tothe tensides and the sequestering agents for copper are assigned to thesequestering builder salts.

The products, according to the invention, can also be usedadvantageously as soaking agents, particularly if the laundry remainsfor a longer time in the solutions of the soaking agents. Such soakingagents have approximately the following composition:

to percent by weight of tensides, including the optionally presentphosphoric acid esters,

95 to 45 percent by weight, preferably 90 to 60 percent, by weight ofpreferably alkaline-reacting builder salts, as well as the optionallypresent corrosion inhibitors and/or the optionally present sequesteringagents for heavy metals,

5 to 50 percent by weight, preferably to 35 percent by weight, of thebleaching component of the invention.

In addition, the below described washing agent ingredients, mostly usedin smaller amounts, may be present in such soaking agents, such asantimicrobial acting compounds, soil suspension agents, enzymes,perfumes, dyes, etc.

Since the effect of the activators is connected with a use of an alkali,the builder salts ought to contain sufficient amounts of stronglyalkaline-reacting salts, such as alkali metal carbonates, in order toprevent a lowering of the pH value of the bleaching or washing liquorbelow the desired value.

A preferred application field of the invention are the cold-bleachingprewashing and washing agents, whose composition lies generally in therange of the following formula:

5 to 40 percent, preferably 7 to 30 percent, by weight of a tensidecomponent, containing at least one tenside from the type of thesulfonates, sulfates, soaps, non-ionics and/or of the phosphoric acidesters as well as, optionally, one or more of the following substances:

0 to 10 percent, preferably 0.5 to 8 percent, by

weight of foam stabilizers,

0 to 10 percent, preferably 0.5 to 8 percent, by

weight of non-surface-active foam inhibitors,

10 to 90 percent, preferably 30 to 55 percent, by weight of sequesteringand/or non-sequestering builder salts, including the alkali metal saltsof weak acids intended for the binding of the acids liberated by theactivator as well as optionally present corrosion inhibitors and/orsequestering agents for heavy metals, whereby at least a part of thesebuilder salts, preferably, the greatest amount, react alkaline, andwhereby the amount of the alkaline to neutral-reacting builder saltspreferably amounts to 0.5 to 7 times, and particularly 1 to 5 times theamount of the total tenside component,

5 to 50 percent, preferably 10 to 35 percent, by weight of the bleachingcomponent according to the invention,

0 to 20 percent, preferably 2 to percent, by weight of other washingagent ingredients, such as textile softeners, corrosion inhibitors,antimicrobial active compounds, soil suspension agents, enzymes,perfumes, dyes, water.

Fine washing agents, to be applied at temperatures up to 70C, whosetenside content is mostly in the range of from 8 to 40 percent,preferably 12 to 40 percent, by weight, also fall within this generalformulation. Insofar as these fine washing agents are not intended foruse in washing machines, particularly in drum-washing machines, theyneed not contain foam inhibitors.

Of particular practical significance are the washing agents, intendedfor the use in washing machines, preferably in drum washing machines, inwhich the tenside component amounts mostly to 7 to 30 percent by weight.The tenside component contains mostly at least one of the threefollowing tenside types in the amounts given:

15 to 99 percent, preferably 35 to percent, by weight of sulfonatesand/or sulfates with preferably 8 to 18 carbon atoms in the hydrophobicmoiety,

10 to 60 percent, preferably 10 to 50 percent, by

weight of non-ionic surface-active compounds,

I to 60 percent, preferably 3 to 50 percent, by weight of phosphoricacid esters as well as, optionally one or several of the followingcompounds:

5 to 70 percent, preferably 10 to 60 percent, by

weight of soap,

0 to 10 percent, preferably 0.5 to 8 percent, by

weight of foam stabilizers,

0 to 10 percent, preferably 0.5 to 8 percent, by

weight of non-surface-active foam inhibitors,

whereby, however, the foaming power of the tenside components is reducedeither by the simultaneous presence of different tensides, diminishingreciprocally the foaming power and/or of foam reducing soap and/or ofnon-surface-active foam inhibitors.

Of the, preferably inorganic, per-compounds yielding H O, in aqueoussolution, sodium perborate tetrahydrate (NaBO,-H O,-3H,O) is of specialpractical importance. Partly or completely dehydrated perborates, i.e.,up to NaBO,.H O,, may be used in its place. Borates such as mam-H 0,described in German Pat. No. 901,287 and US. Pat. No. 2,491,789, inwhich the ratio M 03 0, is less than 0.5 :1 and preferably lies in theregion of 0.4 to 0.15:1, while the ratio H O zNa lies in the region of0.5 to 4:1 are also useful. All these perborates may be wholly or partlyreplaced by other inorganic per-compounds, especially by peroxyhydrates,such as the peroxyhydrates of ortho-, pyroor polyphosphates, especiallyof the tripolyphosphates, as well as the carbonates.

It is advisable to incorporate in the compositions from 0.25 to 10percent by weight of the usual watersoluble and/or water-insolublestabilizers for the stabilization of the per-compounds. Suitablewater-insoluble per-compound stabilizers which, for example, constitute1 to 8 percent, preferably 2 to 7 percent, of the weight of the totalpreparation, are the magnesium silicates (MgOzSiO 4:1 to 1:4, preferably2:1 to 1:2 and especially 1:1), mostly obtained by precipitation fromaqueous solutions. Other alkaline earth metal, cadmium or tin silicatesof corresponding composition are utilizable in their place. Theabove-mentioned organic sequestering agents for copper are useful aswatersoluble per-compound stabilizers.

The activators to be used according to the invention should have,according to the above definition, an activation value of at least 3,preferably of at least 4.5 in the Per-Acid Formation Test.

Per-Acid Formation Test The activation value titre) for the activatorsis determined in the following way:

Solutions which contain 0.615 gm/liter of NaBO," l-l,O,. 3H,O (4mMol/liter) and 2.5 gm/liter of Na O-,'10 H O, are heated to 60C, andthen are mixed with 4 mMol/liter of activator and maintained at the saidtemperature for 5 minutes with stirring. Then 100 ml of this liquid isadded to a mixture of 250 gm of ice and ml of glacial acetic acid andtitrated immediately after addition of 0.35 gm of potassium iodide with0.1 N sodium thiosulfate solution, using starch as indicator. Under thegiven experimental conditions, for a 100 percent activation of theperoxide used, 8.0 ml of 5 thiosulfate solution are consumed, the titreis 8.0. This maximum value is, of course, seldom attained. Goodactivators have a titre of at least 4.5, preferably from 5 to 7. Usefulresults are often obtained with activators having a titre of at least3.0.

Activators of the N-acyl or O-acyl compounds type contain an acylresidue R--CO--, in which R represents optionally substitutedhydrocarbon residues with l to 8 carbon atoms. If the residues R arealiphatic, they preferably have 1 to 3 carbon atoms, and if they arearomatic, they may contain up to 8 carbon atoms. Consequently, theresidue R is preferably one of the following: lower alkyl, such asmethyl, ethyl, N-propyl or isopropyl; phenyl; alkylphenyl such as toluylor xylyl residues. Suitable substituents are C alkoxy groups, halogenatoms, nitro or nitrile groups; when Ris an aromatic residue it may bechloroand/or nitrosubstituted, especially m-chloro or morp-nitrosubstituted. Such substituents are, for example, chloroalkylhaving 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, andp-methoxyphenyl,

Of the activators described below, compounds with a melting point of atleast 70C, preferably at least 100C and especially at least 150C, arespecially suitable. Further the equivalent weight of these compoundsshould be not more than 170, preferably not more than 130 and especiallynot more than 110 (the equivalent weight is here the quotient of themolecular weight and the number of R-CO residues present in the moleculewhere the compound is N-acylated or O- acylated).

The types of compound mentioned under (a) to (l) are useful activatorsaccording to the invention. In the formulae the numbered residues R havethe meaning given for R above unless specifically otherwise indicated.If several residues R are present in a molecule, they may be the same ordifferent.

a. N-diacylated amines of the formula I, in which X represents a residueR or one of the residues la, lb,

or lc.

R c 0 CO-RIS NX -CHr-N R|:-C 0 C O-Ru C O-Rn C O-Rn -CH:CH;N N\

(1b) (IQ) From this class of compounds,N,N,N',N-tetraacetylmethylenediamine (melting point 92-95C), N,N,N,N'-tetraacetylethylenediamine, N,N-diacetylaniline andN,N-diacetyl-ptoluidine are named as examples.

b. N-alkyl-N-sulfonyl-carbonamides of formula ll, in which R,;,preferably signifies a C alkyl residue.

OC-Ru Rn-N 8 Activators of this type are, for example, N-methyl-N-mesylacetylamide (melting point 73-79C). N-methyl-N-mesyl-benzoylamide(m.p.

ll6-l l8.5C), nitrobenzoylamide (m.p.methyl-N-mesyl-p-methoxybenzoylamide ll7l l7.5C).

c. N-acylhydantoins of formula III, in which at least one of theresidues X and X represent an RCO- residue, while the other may alsorepresent a residue R or a carboxymethyl or a lower alkoxycarbonylmethylresidue; Y and Y represent hydrogen or alkyl residues with l to 2 carbonatoms.

N-methyl-N-mesyl-pl59-l60C) and N- C ii (III) Suitable compounds are,for example, l,3-diacetyl- 5,5- dimethylhydantoin,1,3-dipropionylhydantoin (m.p. 104.5to 106C) and3-benzoylhydantoin-lacetic acid ethyl ester.

d. Cyclic Nacylhydrazides of formula W, in which the two nitrogen atomsare part of a 5- or 6- membered hetero-ring from the group of maleicacid hydrazide, phthalic acid hydrazide, triazole or urazole.

N-com, (W)

A suitable compound is, for example, mono-acetylmaleic acid hydrazide.

e. Triacyl-cyanurates of formula VI R or R to give a succinyl orphthalyl residue and n signifies a whole number from O to 2.

Activators of this type are, for example, Obenzoyl-N,N-succinyl-hydroxylamine (m.p. l37l39C),O-acetyl-N,N-succinyl-hydroxylamine (mp. 13 2l 34C),O-p-methoxybenzoyLN,N-succinylhydroxylamine (m.p. l42-l45C), O-p-Tetraacylated glycolurils and especiallytetraacetylnitrobenzoyl-N,N-succinyl-hydroxylamine (m.p. glycoluril(m.p. 233-240C) are preferably used. 2l2 215C) andO,N,N-triacetyl-hydroxylamine. In addition. the following acylatedglycolurils are j. N,N'-diacyl-sulfurylamides of f l VII], i suitable:di-(chloracetyl)-diacetyl-glycoluril (m.p.

which R, and R preferably represent C alkyl 5 267-269C). r pr pi nyl-g yl ri -P- residues or aryl residues such as phenyl, while R l44l46C). m ty -3. ,6-tria etylglycoluril and R preferably represent C alkylresidues, es- -P- 7921 dlacetyldipfoplonylglycol"Til pecially C alkylresidues. (m.p. l44-l46C) and diacetyl-dibenzoylglycoluril (m.p.244249C). The acylated glycolurils are not only of special practicalimpor- N-SO -N tance on account of their excellent properties as R co(vm) activators, but owing to their high melting point they are verysuitable for the preparation of pulver-N,N-dimethyl-N,N'-diacetyl-sulfurylamide (m.p. ulent products which arestable on storage.

58 to 60C) and N,N'-diethyl-N,N'-dipropionyll sulfurylamide (m.p. 9597C)may be mentioned as examples.

It is often sufficient to activate only a part of the active oxygenpresent. For this, additions of activotor of at least 0.05, preferablyof at least 0.1 mol of activator k.l,3-Diacyl-4,5-diacyloxy-lmidazolidmes of forper gram-atom of activeoxygen are sufi'icient. If the mula m whlch represents hydrogen orgreatest possible activation of the active oxygen is re- Rand andrepresent hydrogen or quired, the addition of activator can be increasedup to OCRn 4 mols, preferably up to 3 mols. However, it is preferred towork with 0.3 to 2 mols of activator per gramatom of the active oxygen.These amounts can, of

XPCH H O C course be varied according to the activity of the particmular activator used.

The activators may be provided with a coating of substances which areinert towards the activators. This To these belong: I,3 diformy| 4,5diaccwxy prevents a contact of the activators with the stronglyimidazolidine 16004655: C), l3 diacety} alkaline-reacting alkali metalsilicates, according to the 4,5-diacetoxyimidazolidine (m.p. 139-140.5cabove defimtlom and P y Wlth the Perwmpounds,

O -Rn (1x) l,3-diacetyl-4,5-dipropionyloxy-imidazolidi e whichcontributes to the stability in storage of the prod- (m'p 5 37 ucts ofthe invention. Acylaled SlycOluTlls of the general formula The opticalbrighteners utilized in the compositions Whlch X101 represents theresldue R of the invention are those of the 4,4'-bis-(azolyl)- Rurco xmstilbene-2,2'-disulfonic acid type (I), the stilbyl- 1 naphthotriazoletype (ll), the bis-(benzoxazolyl)- C o derivative type (1"), the2-benzoxazolyl-4,S-naphthol 40 thiophene type (IV), and thediphenyldistyryl type (V). These optical brighteners are compounds ofthe formu- Riwo O-R10I (X): lae selected from the group consisting ofAzolyl CH=CH azolyl l R1 ll1 \N v N i N W R5 0 0 Rs Wm s and o (v)CH=CH- -c H=C H and A represents a member selected from the groupconsisting of hydrogen and SO H, R represents a member selected from thegroup consisting of hydrogen and alkyl having 1 to carbon atoms, Rrepresents a member selected from the group consisting of hydrogen andhalogen, R, represents a member selected from the group consisting ofCN, SO H and SO NHR, R represents a bivalent linkage selected from thegroup consisting of --CH==CH,

X represents a member selected from the group consisting of -NH-, S, andO, R represents a member selected from the group consisting of hydrogen,alkyl having 1 to 5 carbon atoms and phenyl, R and R, represent membersselected from the group consisting of phenyl and phenyl substituted withat least one substituent selected from the group consisting of alkylhaving 1 to 4 carbon atoms, hydroxyalkyl having 2 to 5 carbon atoms,alkoxy having 1 to 5 carbon atoms, chloro, CN, COOH, SO,H, SO,CL andSO,N R,,R,, and R and R, are members selected from the group consistingof hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 2 to4 carbon atoms and, taken together with the nitrogen, piperidino,piperazino, morpholino and pyrrolidino.

Among the compounds of the above formulae are, for example:4,4'-bis-(4-phenyl-vic-tri-azol-Z-yl)- stilbene-2,2'-disulfonic acid andits alkali metal salts such as the sodium salt,4,4-bis-(naphthotriazol-2-yl) stilbene-2,2-disulfonic acid and itssodium salt, 4,4- bis-(S-phenyl-pyrazol-Z-yl)-stilbene-2,2'-disulfonicacid and its sodium salt, 4-(4,5naphthotriazol-2-yl) stilbene-Z-sulfonicacid and its sodium salt, 4-(4,5naphthotriazol-Z-yl)-4'-chlorostilbene-Z-sulfonic acid and its sodiumsalt, 4-(4,5-naphthotriazol-2-yl)- stilbene-Z-sulfamide,2,5-bis-(benzoxazol-2-yl thiophene, l,2-bis-(S-methyI-benzoxazol-Z-ylethylene, 4,4'-bis-(S-phenyl-benzoxazol-Z-yl)-stilbene,2-benzoxazolyl-4,5naphthothioprene, diphenyldistyryl-2,2"disulfonic acidand its sodium salt, diphenyldistyryl-2-chloro-2'-sulfonic acid and itssodium salt, di-2-chlorophenyldistyryl, etc.

The otpical brighteners of formulas l to IV in the compositions of theinvention may be optionally replaced wholly or in part with thediphenyldistyryl compounds of the formula where each of the radicals Ror R may represent a hydrogen atom or a sulfonic acid radical. Like theradicals R and R also the radicals R and R may be identical ordifferent. R and R are phenyl radicals or substituted phenyl radicals,where as substituents the following atoms or atom groups are possible:alkyl, hydroxyalkyl, or alkoxy radicals with l to 5 carbon atoms;furthermore, chloro, nitrile, carboxyl, sulfonic acid, chlorosulfonyl,or sulfonamide radicals, whereby one of the aminohydrogen atoms or bothmay be substituted by alkyl radicals with l to 5 carbon atoms orhydroxyalkyl radicals with 2 to 4 carbon atoms or whereby the amidenitrogen may be part of a heterocyclic ring. Preferably as radicals R orR are chlorophenyl, nitrilo-phenyl, alkylphenyl, hydroxyalkylphenyl,alkoxyphenyl, carboxyphenyl and sulfophenyl, where all these phenylradicals may contain as second substituent also a sulfonic acid group.Like the sulfonic 'acid group, also the substituents Cl, CN and COOH maybe present twice on one phenyl radical. Further R and R may preferablyrepresent the radicals sulfamidophenyl (C,H SO -NH,) andmorpholinosulfophenyl (C H -SO,NC H O).

Insofar as the optical brighteners to be used, according to theinvention, contain sulfonic acids or carboxylic acids, they arepreferably utilized in the form of their water-soluble salts of thealkali metals, ammonium salts or salts of amines or alkylolamines with lto 6 carbon atoms in the molecule.

The products of the invention may also contain combinations of opticalbrighteners of the above-named types. insofar as the products of theinvention are soaking or washing agents, in which the bleachingcomponent, according to the invention, is present in amounts of 5 to 50percent, preferably 10 to 35 percent, by weight, the content of opticalbrightener of these agents lies preferably in the range of 0.002 to 1.5percent by weight.

Triazoles and tetrazoles, known as anti-corrosion agents, with thegroups =Nme or =NOMe, are the following compounds, for instance,benzotriazole, methylbenzotriazole, l,2- and l,8-naphthotriazoles,nitrobenzotriazole, tetrazole, S-aminotetrazole, alkylene-5,5-ditetrazole, 5-alkylenetetrazoles, S-dialkylaminotetrazoles, and5alkyl-4-hydroxytetrazoles, where the alkyl or alkylene radicals maycontain 1 to 5 carbon atoms.

Triazoles that contain an aromatic nucleus, such as a benzene ornapthalene nucleus, are particularly effective. For this reason, for thepractical application benzotriazole and the naphthotriazoles arepreferred.

The organic sequestering agents for heavy metals include thewater-soluble, preferably alkali metal salts of aminotriacetic acid,ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid andaminotriethylidene-diphosphonic acid. In their place also othersequestering agents may be used, insofar as their sequestering power,particularly for copper, is not substantially below that of the namedcompounds.

The named sequestering agents have already been recommended as organicbuilder salts for soaking, prewashing and washing agents. For thisreason, the above application amounts for these sequestering agents areonly valid in the case that not already larger amounts of suchsequestering agents are already present as organic builder salts.

The higher fatty alcohols or their ethoxylation products, used for thepreparation of the ortho-, pyroor polyphosphoric acid partial esters,are substantially the same as are also used for the preparation of othertensides. In this connection, the following enumeration of the synthetictensides, optionally contained in the products of the invention are tobe considered.

These phosphoric acid esters" may be prepared according to various knownprocedures, such as by direct esterification of the alcohol componentwith the correspoonding acids of phosphorus, with the halogenderivatives of phosphorus or with the corresponding phosphoric acidanhydrides, particularly with phosphorus pentoxide.

Above all the last-named reaction represents a practically usefulpreparation method for such esters. By this reaction, in addition to thepartial esters of orthophosphoric acid also partial esters of anhydricacids of phosphorus are formed, particularly of the pyroandpolyphosphoric acids, where, however, the esters of ortho-phosphoricacid, optionally also the esters of orthoand pyro-phosphoric acidsrepresent the main product. The salts of the partial esters of the namedacids, to be used according to the invention, may contain on eachphosphorus atom, one or two higher fatty alcohol radicals bound as anester. Often in the transesterification of fatty alcohols or of theiralkoxylation products, mixtures of esters are formed with one or withtwo alcohol radicals per phosphorus atom.

Preferably the partial esters of phosphoric acid have the formula A-O ol o-H V A-O wherein A is a member selected from the group consisting ofhydrogen and with the proviso that one A may be hydrogen, R, is a memberselected from the group consisting of hydrogen and methyl, R, is a fattyalcohol residue having from to 22 carbon atoms, and n is an integer from0 to 10. These partial esters of phosphoric acid are utilized in theform of their water-soluble salts, especially their alkali metal andammonium salts where the hydrogen of A is replaced by alkali metal orammonium, or their mono-, dior triethanolamine salts.

The salts of orthophosphoric acid diesters of ethoxyl ated fattyalcohols, with 2 to 6 ethyleneglycol ether radicals in the molecule, forinstance, as obtained from coconut, palm kernel or tallow fatty acids,with 12 to 18 carbon atoms in the fatty alcohol radical have been provenpreferable.

These partial esters of phosphoric acids also have tenside propertiesand may, therefore, be utilized in larger amounts as such than would benecessary from the point of view of corrosion protection.

The products of the invention can be prepared by all procedures,customary in the production of oxidizing agents, bleaching agents,washing auxiliaries and washing agents. For instance, the singleingredients can be mixed with each other in a dry, powdery or granularstate. These mixtures can be granulated or agglomerated, according toknown processes, by spraying them, while being agitated, with water orwith aqueous solutions containing active substances. This process isabove all recommended when anhydrous salts are present in the mixturethat crystallize with binding of water of crystallization.

in all of these processes it is recommended to avoid a direct contact ofthe activators and percompounds in the presence of water, since theactivator effect already takes place at that time, and a part of theactivators or of the active oxygen is consumed.

This is particularly valid for the heat-drying processes, customary inthe production of washing auxiliaries and washing agents. Mostly onlythose ingredients are incorporated into the aqueous charge to beheatdried, that are not changed by water and/or heat, and the otheringredients are admixed with the thusobtained initial powder. In theprocess, it is immaterial for the effect of the combinations of theinvention in which partial powder the single ingredients are present.Thus, for instance, the phosphoric acid esters of optionally ethoxylatedfatty alcohols and the sequestering agents can be incorporated, togetherwith the other ingredients of the product, particularly of washingauxiliary or washing agents, into an aqueous charge and then by knownprocesses, preferably by heat drying, transformed to a powder. Thispowder is then mixed with the other ingredients, sensitive to moistureand/or heat, such as the activator, the percompound and optionallyother, for the same reason separately to be incorporated, ingredients,such as enzymes.

An enumeration of the other ingredients present in the products of theinvention, particularly in the washing auxiliaries and washing agents,such as tensides, builders, soil suspension agents, enzymes, etc.follows.

The anionic, amphoteric or non-ionic tensides contain in the molecule atleast one y p UBic residue mostly containing 8 to 26, preferably 10 to22 and especially 10 to 18, carbon atoms and at least one anionic,non-ionic or amphoteric water-solubilizing group. The preferablysaturated hydrophobic residue is mostly aliphatic, but possibly alsoalicyclic in nature. it may be combined directly with thewater-solubilizing group or through intermediate members. Suitableintermediate members are, for example, benzene rings, carboxylic acidester or carboxylic acid amide groups, residues of polyhdric alcoholslinked in ether or esterlike form, such as, for example, those ofethylene glycol, propylene glycol, glycerine or corresponding polyetherresidues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residuewith 10 to 18, preferably 12 to l 8, carbon atoms but deviations fromthe preferred range of carbon atoms are possible, depending on thenature of the surface-active compound in question.

Soaps from natural or synthetic fatty acids, possibly also from resin ornaphthenic acids, are utilizable as anionic detergent substances,especially when these acids have iodine values of not more than 30, andpreferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates andsulfates possess special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates,especially alkylbenzene sulfonates, which are obtained from preferablystraight-chain aliphatic hydrocarbons having 9 to 15, especially 10 to14 carbon atoms, by chlorinating and alkylating benzene or fromcorresponding terminal or non-terminal olefins by alkylation of benzeneand sulfonation of the alkylben zenes obtained. Further, aliphaticsulfonates are of interest, such as are obtainable, for example, frompreferably saturated hydrocarbons containing 8 to 18 and preferably 12to 18 carbon atoms in the molecule by sulfochlorination with sulfurdioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen,and conversion of the products thereby obtained into the sulfonates. Asaliphatic sulfonates, mixtures containing alkene sulfonates,hydroxyalkane sulfonates and disulfonates are useful, which are obtainedfrom terminal or non-terminal C and preferably C1248 olefins bysulfonation with sulfur trioxide and acid or alkaline hydrolysis of thesulfonation products. in the aliphatic sulfonates thus prepared, thesulfonate group is frequently found attached to a secondary carbon atom;however, sulfonates with a terminal sulfonate group obtained by reactionof terminal olefins with bisulfite can also be used.

Furthermore, salts, preferably dialkali metal salts of a-sulfo-fattyacids, and aalts of esters of these acids with monoor poly-hydricalcohols containing 1 to 4, and preferably 1 to 2 carbon atoms belong tothe sulfonates to be used according to the invention.

Further useful sulfonates are salts of fatty acid esters ofhydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the saltsof the fatty alcohol esters of lower aliphatic or aromatic sulfomonoordi-carboxylie acids containing 1 to 8 carbon atoms, alkylglycerylethersulfonates and the salts of the amide-like condensation products offatty acids or sulfonic acids with aminoethane-sulfonic acid.

As tensides of the sulfate type are fatty alcohol sulfates, especiallythose prepared from coconut fat alcohols, tallow fat alcohols or oleylalcohol. Useful sulfonation products of the sulfate type are alsoobtainable from terminal or non-terminal C olefins. Sulfated fatty acidalkylolamides or fatty acid monoglycerides, and sulfated alkoxylationproducts of alkylphenols (C alkyl), fatty alcohols, fatty acid amides orfatty acid alkylolamides, which may contain in the molecule 0.5 to 20,preferably 1 to 8 and especially 2 to 4 ethylene and/or propylene glycolresidues, also belong to this group of surface-active compounds.

Suitable anionic surface-active compounds of the carboxylate type arethe fatty acid esters of fatty alcohol ethers of hydroxycarboxylicacids, and the amidelike condensation products of fatty acids orsulfonic acids with aminocarboxylic acids, for example, with glycocoll,sarcosin or protein hydrolysates.

The non-ionic surface-active compounds, here called non-ionics," for thesake of simplicity, include products whic e their solubility in water tothe presence of polyether chains, amineoxide, sulfoxide, or'phosphine-oxide groups, alkylolamide groups and very generally, to anaccumulation of hydroxyl groups.

The products obtainable by addition of ethylene oxide and/or glycide tofatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid andsulfonic acid amides are of special practical interest. These nonionicsmay contain per molecule 4 to 100, preferably 6 to 40 and especially 8to ether residues, particularly ethylene glycol ether residues.Moreover, propylene or butylene glycol ether residues or polyetherchains may be present in or at the ends of these polyether residues.

Further, products known by the trade name of Pluronics" or Tetronics"belong to the non-ionics. They are obtained from water-m I e glycols orfrom water-insoluble propoxylated lower aliphatic alcohols containing 1to 8, preferably 3 to 6 carbon atoms and/or from water-insolublepropoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic)propylene oxide derivatives are converted into the said non-ionics byethoxylation until they become soluble in water. Finally, the reactionproducts of the above-mentioned aliphatic alcohols with propylene oxideknown as Ucon-Fluid" some of which are still water-soluble, are usefulas non-ionics.

The non-ionics also include fatty acid or sulfonic acid alkylolamideswhich are derived, for example, from monoor di-ethanolamine,dihydroxypropylamine or other polyhydroxyalkylamines, for example theglycamines. They can be replaced by amides from higher primary orsecondary alkylamines and polyhydroxycarboxylic acids.

The surface-active amineoxides include, for example,

the products derived from higher tertiary amines having a hydrophobicalkyl residue and two shorter alkyl and/or alkylol residues containingup to 4 carbon atoms, each.

Amphoteric surface active compounds contain in the molecule both acidand basic hydrophilic groups. Carboxyl, sulfonic acid, sulfonic acidhalf ester, phosphonic acid and phosphoric acid partial ester groups arethe acid groups. Basic groups include primary, secondary, tertiary andquaternary ammonium groups. Amphoteric compounds with quaternaryammonium groups belong to the betaine type.

Carboxy, sulfate and sulfonate betaines have particular practicalinterest on account of their good compatibility with othersurface-active compounds. Suitable sulfobetaines are obtained, forexample, by reacting tertiary amines containing at least one hydrophobicalkyl residue with sultones, for example propaneor butane-sultone.Corresponding carboxybetaines are obtained by reacting the said tertiaryamines with chloracetic acid, or its salts or with chloracetic acidesters and splitting the ester linkage.

The foaming power of the surface-active compounds can be increased orreduced by combination of suitable types of surface-active compounds,just as it can be changed by additions of non surface-active organicsubstances.

Suitable foam stabilizers, above all in the case of surface-activecompounds of the sulfonate or sulfate type, are surface-active carboxyor sulfo-betaines and also the above-mentioned non-ionics of thealkylolamide type. Moreover, fatty alcohols or higher terminal diols canbe utilized for this purpose.

Products with a reduced foaming power are primarily intended for use inwashing and dishwashing machines, where sometimes a limited repressionof foam is sufficient while in other cases a stronger foam repressionmay be desired. Products which foam in the middle range of termperatureup to about 65C, but at higher temperatures to l00C) develop less andless foam are of special practical importance.

A reduced foaming power is frequently obtained with combinations ofdifferent types of surface-active compounds, especially withcombinations of synthetic anionic surface-active compounds, particularlyof l sulfates and/or sulfonates or of (2) non-ionics on the one hand and(3) soaps on the other hand. With combinations of the components (1) and(2) or (I), (2) and (3), the foaming power can be affected by theparticular soap used. The inhibition of foam is smaller with soaps frompreferably saturated fatty acids with 12 to l8 carbon atoms, while agreater inhibition of foaming, particularly in the higher temperaturerange, is obtained by soaps from saturated fatty acid mixtures having 20to 26, preferably 20 to 22 carbon atoms, used in an amount of from 5 topercent by weight of the total soap fraction present in the combinationof surface-active compounds.

The foaming power of the surface-active compounds can also be reduced,by the addition of known, nonsurface-active foam inhibitors. Theseinclude optionally chlorine-containing N-alkylated aminotriazines, whichare obtained by reacting 1 mol of cyanuric chloride with 2 to 3 mols ofa monoand/or di-alkylamine having 6 to 20, preferably 8 to 18 carbonatoms in the alkyl residue. Aminotriazine or melamine derivatives whichcontain propylene glycol or butylene glycol ether chains, in an amountof 10 to 100 of such glycol residues per molecule, have a similaraction. Such compounds are obtained, for example, by addition ofcorresponding amounts of propylene and/or butylene oxide toaminotriazines, especially to melamine. The reaction products from 1 molof melamine with at least mol of propylene oxide or at least 10 mol ofbutylene oxide are preferred. Products which are obtained by addition of5 to 10 mol of propylene oxide to 1 mol of melamine and further additionof ID to 50 mol of butylene oxide to this propylene oxide derivativehave proved particularly effective.

Other non-surface-active water-insoluble organic compounds, such asparaffms or halogenated paraff'ms with melting points below 100C,aliphatic C to C ketones and aliphatic carboxylic acid esters, whichcontain at least 18 carbon atoms in the acid or alcohol residue,possibly also in both of these two residues (for example triglyceridesor fatty acid-fatty alcohol esters), can be used as foam inhibitors,particularly in combinations of anionic synthetic surface-activecompounds and soaps.

The non-surface-active foam inhibitors are frequently only completelyeffective at temperatures at which they are present in the liquid state,so that the foaming behaviour of the products can be controlled bychoice of suitable foam inhibitors in a similar way to that by thechoice of soaps from fatty acids of suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upontemperature, good foaming products are obtained at lower temperatureswhich, as the temperature approaches the boiling temperature, foam lessand less.

Suitable weakly-foaming non-ionics, which can be used both alone and incombination with anionic, amphoteric and non-ionic surface-activecompounds and which reduce the foaming power of more strongly foamingsurface-active compounds, are products of addition of propylene oxide tothe above-described surface-active polyethylene glycol ethers as well asthe also above-described Pluronic, Tetronic and Ucon- Fluid types.

Suitable builders are weakly acid, neutral and alkaline reactinginorganic or organic salts, especially inorganic or organiccomplex-foaming substances.

Useful, weakly acid, neutral or alkaline reacting salts according to theinvention are, for example, the alkali metal bicarbonates, carbonates,borates or silicates, mono-, dior tri-alkali metal orthophosphates, diortetra-alkali metal pyrophosphates, alkali metal metaphosphates known ascomplex-forming substances, alkali metal sulfates and the alkali metalsalts of organic. non-surface-active sulfonic acids, carboxylic acidsand sulfocarboxylic acids containing 1 to 8 carbon atoms. These include,for example, water-soluble salts of benzene-, tolueneor xylene-sulfonicacid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid orsalts of sulfodicarboxylic acids and the salts of acetic acid, lacticacid, citric acid and tartaric acid.

Further, the water-soluble salts of higher molecular weightpolycarboxylic acids are utilizable as builders, especiallypolymerizates of maleic acid, itaconic acid, mesaconic acid, fumaricacid, aconitic acid, methylene-malonic acid and citraconic acid.Copolymerizates of these acids with one another or with otherpolymerizable substances, as for example, with ethylene, propylene,acrylic acid, methacrylic acid, crotonic acid, 3-butene-carboxylic acid,3-methyl-3- butenecarboxylic acid and with vinyl methyl ether, vinylacetate, isobutylene, acrylamide and styrene, are utilizable.

Suitable complex-forming builders are also the weakly acid reactingmetaphosphates and the alkaline reacting polyphosphates, especiallytripolyphosphate,

in the form of their alkali metal salts. They may be wholly or partlyreplaced by organic complex forming substances.

The organic complex-forming substances include, for

polyamine-N-polycarboxylic acids and other known organic complex-formingsubstances, while com binationsof different complex-forming substancesmay also be used. Diand poly-phosphonic acids of the followingconstitutions also belong to the other known complexforming substances:

YL (5H H(|) XL Y 0H 1 in which R represents alkyl and R alkyleneradicals with 1 to 8, preferably 1 to 4 carbon atoms, X and Y representhydrogen or alkyl radicals with l to 4 carbon atoms and Z represents OH,NH, or NXR. For a practical application above all the followingcompounds are considered: methylene-diphosphonic acid, l-hydroxyethanell -diphosphonic acid, 1- aminoethane- 1 l -diphosphonic acid, amino-tri-(methylene-phosphonic acid), methylaminoorethylamino-di-(methylene-phosphonic acid as well asethylenediamine-tetra-(methylene-phosphonic acid). All these complexingcompounds may be present as free acids or preferably as the alkali metalsalts.

Further, soil suspending agents or greying inhibitors may be containedin the preparations according to the invention, which hold the dirtloosened from the fiber suspended in the bath and thus prevent greying.Watersoluble colloids of mostly organic nature are suitable for thispurpose, for example, the water-soluble salts of polymeric carboxylicacids, glue, gelatine, salts of ether-carboxylic acids or ether-sulfonicacids of starch or cellulose or salts of acid sulfuric acid esters ofcellulose or starch. Water-soluble polyarnides containing acid groupsare also suitable for this purpose. Furthermore, soluble starchpreparations and starch products other than those mentioned above can beused, for example, degraded starch, and aldehyde starches.Polyvinylpyrrolidone is also useful.

The constituents of the bleaching treatment compositions according tothe invention, especially washing compositions and washing assistants ofthis kind, and particularly the builder substances, are usually chosenso that the preparations have a neutral to distinctly alkaline reaction,so that the pH value of a 1 percent solution of the preparation mostlylie in the region from 7 to 12. Fine washing compositions usually have aneutral to weakly alkaline reaction (pH value 7 to 9.5), while soaking,prewashing and boiling washing compositions are adjusted to be morestrongly alkaline (pH value 9.5 to 12, preferably 9.5 to 10.5). Theaction of the activators is combined with a certain consumption ofalkali. Therefore, it has been already recommended to incorporatestrongly alkaline-reacting builder salts, such as alkali metalcarbonates in order to bind the acid liberated or to buffer the liquorsufficiently to prevent the pH value from falling below the givenminimum val ues during the whole period of treatment.

The enzymes to be used are mostly a mixture of different enzymicsubstances. They are called proteases, amylases, carbohydrases,esterases, lipases, oxidoreductases, catalases, peroxidases, ureases,isomerases, lyases, transferases, desmolases or nucleases, dependingupon their action. The enzymic substances obtained from strains ofbacteria of fungi such as Bacillus subtilis and Streptomyces griseus areof particular interest, especially proteases or amylases. Preparationsobtained from Bacillus subtilis have the advantage compared with othersthat they are relatively stable towards alkali, percompounds and anionicdetergent substances and are still active at temperatures up to 70C.

Enzyme preparations are usually marketed by the manufacturers as aqueoussolutions of the active substances or with the addition of diluents, aspowders. Suitable diluents are sodium sulfate, sodium chloride, alkalimetal ortho-, pyroor polyphosphates, especially tripolyphosphate.Frequently moist enzyme preparations are mixed with calcined salts,which then bind water of crystallization present and the enzymicsubstance, possibly with agglomeration of the particles to largerparticles.

When the enzymic substances are present as dry powders, liquid,paste-like and possibly also solid, nonionic, preferably surface-active,organic compounds, especially the above-described non-ionics, can beused at the usual room temperatures to bind the enzymes to the powdersof the washing compositions or washing assistants. For this purpose amixture of the respective product and the enzymic substance ispreferably sprayed with the above-mentioned non-ionic substances, or theenzyme preparations is dispersed in the said non-ionic substance andthis dispersion is united with the other constituents of the product.When these other constituents are solids, the dispersion of the en zymicsubstances in the nonionic component can also be sprayed on the othersolid constituents. The enzymes may also be incorporated as granulatesor as products dispersible in cold solutions. Such enzyme preparationsare coated and thus protected against a rapid loss of activity.

The enzymes, or combinations of enzymes with different actions, aregenerally used in quantities such that the finished products haveprotease activities of 50 to 5,000, preferably to 2,500 LVE/g and/oramylases activities of 20 to 5,000, preferably 50 to 2,000 SKBE/g and/orlipase activities of 2 to 1,000, preferably 5 to 500 lE/g.

These data on enzyme activities result from the activities of thoseenzyme preparations which at the present time seem to be suitable fromthe economic standpoint for use in the washing composition field. Fromthe chemical-technical standpoint the enzyme activities of thepreparations can be increased as desired, so that the activities in thecase of proteases and amylases may be raised, for example, up to fivetimes, and in the case oflipases, for example, up to ten times, thehighest values given above. If, therefore, in the future preparationswith such high activities should be available which also economicallyappear appropriate for the use in the application fields, named at thebeginning, products with respective higher enzyme activities can beprepared.

With reference to the determination of the enzyme activities, thefollowing literature references are given: Determination of the activityof proteases according to Lohlein-Volhard:

' A.Kunzel, "Chemical Tanning Pocketbook," 6th Ed., Dresden and Leipzig,1955; Determination of the activity of amylases:

J. Wohlgemuth, Biochemische Zeitschrift," Vol. 9,

(1908), pp. l-9; R. M. Sandstedt et al., Cereal Chemistry," Vol. 16,

(1939), PP. 712-723; Determination of the activity of lipases:

R. Willstatter et al., Hoppe-Seyler's Zeitschrift ftlr PhysiologicheChemie," Vol. 1923), pp. 1 10-1 17; R. Boissonas, Helvetica ChimicaActa, Vol. 31

The products according to the invention may also contain antimicrobialsubstances. As such, the 2-hydroxy-2', 4,4'-trichloro-diphenylether hasbeen proven good.

The following examples illustrate the practice of the invention withoutbeing limitative in any respect.

EXAMPLES The salt-like constituents contained in the following, such assalt-like surface-active compounds, other organic salts as well asinorganic salts, are present as the sodium salts, unless otherwisestated. The expressions and abbreviations used have the followingmeanings:

ABS" is the salt of an alkylbenzene sulfonic acid with 10 to 15,preferably 1 rt l3,"carbon atoms in-the alkyl chain, obtained bycondensing straight-chain olefins with benzene and sulfonating thealkylbenzene thus formed.

Alkanesulfonate is a sulfonate obtained from par- 21 affins with 12 to16 carbon atoms by the sulfoxidation method.

HPK-sulfonate" of HT-sulfonate" are the sulfonates in the a-position,obtained from the methyl esters of a hardened palm kernel fatty acid ora hardened tallow fatty acid by sulfonation with S0,.

Olefin sulfonate" is a sulfonate obtained from mixtures of olefins with12 to 18 carbon atoms by sulfonating with S0, and hydrolyzing thesulfonation product with an alkaline liquor, which sulfonate consistssubstantially of alkenesulfonate and hydroxyalkanesulfonate, butcontains in addition small quantities of disulfonates. Products areuseful which have been made from aor from non-terminal olefins.

RA-sulfate" and TA-sulfate" are the salts of sulfated substantiallysaturated fatty alcohols, prepared by reduction of coconut fatty acidand tallow fatty acid, respectively.

KA-EO-sulfate is the sulfated product of addition of 2 mols of ethyleneoxide to 1 mol of fatty alcohol.

KA-EO-phosphate" or TA-EO-phosphate are the orthophosphoric aciddiesters of the addition products of about 4 mols ethylene oxide to 1mol of coconut or tallow alcohol. When these tensides are utilized asthe diethanolamine or triethanolamine salts, the percentage figures inthe table are marked by a (D) or (T), respectively.

A E0", KA E0" or Fs-amide 8 E0 are the addition products of ethyleneoxide (E0) to technical oleyl alcohol (0A) or coconut alcohol (KA) orcoconut fatty acid amide, respectively, where the numbers represent themolar amounts of ethylene oxide added to 1 mol of starting material.

KA 9 E0 12 PO" is a non-ionic obtained by re action of 1 mol ofKA 9 E0with 12 mols of propylene oxide.

Carboxybetaine" or Sulfobetaine" are the betaines obtained by reactionof 1 mol of coconut alkyldimethylamine with 1 mol of chloroacetic acidor with 1 mol of propanesultone, respectively.

CMC" is the salt of carboxymethylcellulose.

NTA," EDTA," DETP, HEDP," or ATMP" are the salts of nitrilotriaceticacid, ethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, hydroxyethanediphosphonic acid or aminotrimethylene phosphonicacid, respectively.

The composition of fatty acid mixture from which the Soaps B, C and Dwas prepared, and the composition of fatty acid mixtures the Soap Gwhich may be used instead of the other soaps, are seen from thefollowing Table I.

If the Soaps B, C and D in the formulations given below are replaced bythe same quantity of the Soap G, washing compositions are obtained inwhich the foaming is somewhat less strongly inhibited than thecorresponding composition with the soaps B and C but more strongly thanwith the soap D.

Together with these soaps or in place of them. nonsurface-active foaminhibitors can be used. for exam ple, a mixture of about 45 percent of adi(alkylamino)- monochlorotriazine and about 55 percent of a N,N,N"-trialkylmelamine. In all these triazine derivatives the alkyl residuemay be present as mixtures of homologs with 8 to 18 carbon atoms. Themonochlorotriazine derivative or trialkylmelamine can also be used witha similar result. Provided the described washing compositions containsynthetic sulfates of sulfonates together with soap, the othernon-surface-active foam inhibitors mentioned in the description can beused, as for example, parafiin oil or paraffin. It is advisable toincorporate the non-surface-active foam inhibitor used separately in thewashing composition, for example, dissolved in a suitable organicsolvent or sprayed in the molten state on the moving powder by means ofa nozzle.

Perborate (mono) or perborate (tetra)" are a perborate monohydrate orperborate tetrahydrate of the approximate compositions NaBO,-H,O, or Na80," H20g'3 H20.

TAGU is tetraacetylglycoluril.

The products described in the examples contained the following opticalbrighteners:

Brightener l The sodium salt of the 4,4'-bis-(4-phenyl-vic-tri-azol-2-yl)-stilbene- 2,2'-disulfonic acid of the formula Brightener lll2,5-bis-( benzoxazol-Z-yl)-thiophene Brightener IV l,2-bis-(5-methylbenzoxazol-2-yl)-ethylene Brightener V2-benzoxa2o1y1-4,S-naphthothiophene Napbthyl Brightener Vla The sodiumsalt of a diphenyl-distyryl-disulfonic acid VNBOI OzNa Brightener VlbThe sodium salt of a chloro-diphenyl-distyrylmonosulfonic acid of thestructure:

dichloro-diphenyl-distyryl of the structure:

Brightener VIc Ingredients of the preparaation Perborute TAGUKA-EO-Phosphate TA-EO-Phosphate EDTA ATMP BENZOTRIAZOLE NaJHO,

Na CO, Brightener Vla Brightener Vlb Brightencr Vlc Ingredients of thepreparation Perborate TAG U KA-EO-Phosphate EDTA DETPAMethylbenzotriazole 1 ,8 Naphto- Ingredients of the preparationPerborate TAGU KA-EO-Phosphate TA-EO-Phosphate EDTA ATMP BenzotriazoleNaJ O, Na,CO; Brightener 1 Brightencr 11 Brightener I11 Brightener IVBrightener V Ingredients of the preparation Perborate TAGUKA-EO-Phosphate EDTA DETPA Methylbenzotriazole 1.8-N11phthotriuoleBrightener I Brightener II Brightener I11 Brightener IV Brightener VTABLE II I: by weight of ingredients in example B1 B2 83 41.0 36.1 41.0(U 23.0 19.7 21.3

TABLE 111 k by weight of ingredients in example B6 B7 88 43.5 44.8 38.023.3 46.3 22.8

triazole Na P,O, Na,CO, Brightener VIa Brightener Vlb Brightener VICTABLE IV I by weight of ingredients in example B1 1 B12 B13 41.0 36.141.0 23.0 19.7 21.3

TABLE V k by weight of ingredients in example B16 B17 B18 43.5 44.8 38.023.3 46.3 22.8

B14 B15 42.6 38.1 [ml (ml 43.5 16.5

B19 820 47.1 32.2 (m) 10.1 24.8 23.6 3.5 (T) The composition of somewashing agents, according to the invention are described in Examples W1to W20 in Tables VII to IX.

Ingredients of the preparation ABS HPK-Sulfonate Olefinsulfonate Soap BSoap D KA-EO-Phosphate TA-EO-Phosphate 0A 10 E0 KA 20 E0 KA 9 E0 12 POFs-amide+ 8 E0 Foam inhibitor t z m Na,0.3.3SiO, Na,CO;,

Na,SO.

NTA

EDTA

HEDP

ATMP

CMC

Mg S10, Perborate TAGU Benzotriazole Brightener I Brightener IIBrightener I11 Brightener IV Brightener V Residue Water TABLE VI 1: byweight of ingredients in example W1 W2 W2 6.1 4.9 1.2

' Ingredients of the preparation ABS Alkanesulfonate l-lT-SulfonateKA-Sulfate TA-sulfate KA-EO-Sulfate Soap C KA-EO-Phosphate A 10 E0 KA 9E0 12 PO Clrboxybetaine Sult'obetaine Foam Inhibitor NIIPIO 1e Na,0.3,3S10, Na,CO, Na,SO

CMC NTA EDTA DETP HEDP ATMP MgSiO, Perborate TAGU Methylbenzotriazole1,8-Naphthotriazole Brightener I Brightener l1 Brightener lll Brightener1V Brightener V Residue Water Ingredients of the prepara' tion ABSl-ll'K-Sulfonate Olefinsulfonate Soap B Soap D KA-EO-PhosphateTA-EO-Phosphate 0A 10 E0 KA 20 E0 Fs-amide 8 E0 Foam inhibitor Na,P,O,.Na,0.3.3 SiO, Na,CO,

NTA

EDTA

HEDP

ATMP

CMC

MgSiO, Perborate TAGU Benzotriazole Brightener Vla Brightener VlbBrightencr Vlc Residue Water Ingredients of the preparation ABSAlkanesulfonate HT-Suli'onale KA-Sulfate TA-Sulfate KA-EO-Sulfate Soap CKA-EO-Phosphate 0A 10 E0 KA 9 E0 25 TABLE V11 by weight of ingredientsin example W6 W7 W8 5.3 5.0 2.9

TABLE V111 L by weight of ingredient-I in example W11 W12 W13 6.1 4.91.2

TABLE 1X by weight of ingredients in example W16 W17 W18 12 P0 1.8Carboxybetainc 0.5 Sultobetaine 0.7 06

Foam inhibitor 0.5 0.5 0.6 0.4 Na,P,O,. 32.6 34.2 41.1 36.1 Na,0.3,3SiO, 5.5 3.4 4.0 4.5 Na,CO, 14.8 16.2 14.1 Na,SO. 0.4 0.2 2.5 0.4 CMC1.6 1.3 1.7 1.0 NTA 15.0 15.0 EDTA 0.2 DETP 0.2 HEDP 14.0 4.0 7.0 9.0ATMP 0.2 MgSiO, 2.5 2.0 Perborlte 19.0 14.0 10.0 14.0 15.6

(m) (m) (m) TAGU 10.2 14.0 6.0 3.0 15.6 Methylbenzotriazole 0.2

LS-Naphthotriazole 0.2 Brightener Vla 0.2 0.5 0.1 Brightener Vlb 0.050.15 0.1 Brightener Vlc 0.13 0.15 0.28 0.1

Residue Water 1f textiles of cotton or polyamide are washed or bleachedwith the use of the bleaching and washing agents, described in theexamples, an excellent degree of whiteness is attained even below theboiling temperature. This represents the prerequisite for a satisfactoryeffect of the optical brighteners. The optical brighteners, to beutilized, according to the invention, are not damaged, although withother optical brightener types, a damage by percompounds and activatorsoccurs. This advantage of the product of the invention is particularlyobserved, when there are traces of heavy metals in the treatment liquorsand/or if the liquors were prepared some time before the addition of thetextile goods to be treated. The described advantages are present alsoif the pl-l-value is somewhat lowered by the carboxylic acid formed fromthe activator. Since above all in white linen a lowering of thepl-l-value is not advisable, the products of the invention may containalkaline-reacting salts, as required for the neutralization of thecarboxylic acids formed.

11', in the agents of the Examples B1 to B20 and W1 to W20, thetetraacetylglycoluril contained therein is replaced by the correspondingamounts of tetrapropionylglycoluril, methyl-triacetyl-glycoluril,diacetyldibenzoyl-glycoluril, diacetylaniline, diacetyltoluidine,diacetyl-dimethyl-hydantoin, tetraacetylmethylenediamine ortetraacetyl-ethylene-diamine, similar results are obtained. However, theperborate is better activated by the acylated glycolurils than by theother activators.

The products, according to the above Examples B1 to B20 or Wl to W20contain, in some instances, a deficiency in amounts of activator; thatis, not all of the active oxygen contained in the perborate, isactivated. Work with such preparations is then advantageous, if theeffect of the activators is to be utilized at lower temperatures, inorder to continue the bleaching at higher temperatures with the activeoxygen still present. In such a procedure the amount of activator may bereduced, for instance, up to 5 percent of the carrier of active oxygenpresent.

The preceding examples are illustrative of the practice of theinvention. It is to be understood, however, that other expedients knownto those skilled in the art, or disclosed herein, may be employedwithout departing from the spirit of the invention or the scope of theappended claims.

We claim:

N/ Q -N/ N/ W R and 1. A bleaching component composition useful in anaqueous cold-bleaching treatment consisting essentially of (a) from 95to 99.9 percent by weight ofa mixture of (i) a water-soluble inorganicpercompound yielding H O, in aqueous solution and (ii) an activator foractive oxygen having the formula wherein R R and R represent a memberselected from the group consisting of alkyl having l to 3 carbon atoms,haloalkyl having 1 to 3 carbon atoms, phenyl, and phenylalkyl having 7to 8 carbon atoms and X represents a member selected from the groupconsisting of R and R -CO said activator having an activating action ofat least 3 in the Per-Acid Formation test, said percompound and saidactivator being present in such a ratio that from 0.01 to 4 mols of saidactivator are present for each gram-atom of active oxygen in saidpercompound, and (b) from 0.01 to 5 percent by weight of at least oneoptical brightener having a formula selected from the group consistingof Azolylher selected from the group consisting of hydrogen and halogen,R, represents a member selected from the group consisting of CN, SO,Hand SO,NHR, FL represents a bivalent linkage selected from the groupconsisting of CH=CH-,

CH=CH, Gabonand R R and R and R, are members selected from the groupconsisting of hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkylhaving 2 to 4 carbon atoms and, taken together with the nitrogen,piperidino, piperazino, morpholino and pyrrolidino, and watersolublesalts thereof.

2. The composition of claim 1 containing from 99.98 to 97,5 percent byweight of component (a) mixture and 0.02 to 2.5 percent by weight ofcomponent (b) optical brightener.

3. The composition of claim 2 wherein said activator for active oxygenhas an activating action of at least 4.5 in the Per-Acid Formation Testand said percompound and said activator are present in such a ratio thatfrom 0.05 to 2 mols of said activator are present for each gram-atom ofactive oxygen in said percompound.

4. The composition of claim 3 wherein said percompound yielding H,O inaqueous solution is a water soluble perborate.

5. The composition of claim 1 having an addition content, based on saidtotal composition, of at least one compound selected (1) from 0 to 5percent by weight of a corrosion inhibitor selected from the groupconsisting of triazoles and tetrazoles containing at least one of thegroups =Nme and =NOMe where Me represents a metal or a hydrogen atomreplaceable by a metal, (2)

Re A A B1 wherein azolyl represents an azole structure of the 55 from 0to 20% by weight of water-soluble salts of parformula selected from thegroup consisting of A represents a member selected from the groupconsisting of hydrogen and SO H, R represents a member selected from thegroup consisting of hydrogen and alkyl having l to 5 carbon atoms, Rrepresents a memtial esters of fatty alcohols having 10 to 22 carbonatoms and their ethoxylated and propoxylated compounds having 1 to 10alkoxyl groups, with orthophosphoric acid, pyrophosphoric acid andpolyphosphoric acid, and (3) from 0 to 10 percent by weight of anorganic sequestering builder salt for heavy metals.

6. The composition of claim 5 wherein said watersoluble salts of partialesters has the formula tially of the steps of adding to an aqueoussolution con- 29 30 wherein A is a member selected from the groupconsistrepresents a bivalent linkage selected from the group ing ofhydrogen and consisting of CH=CH'.

with the proviso that one A may be hydrogen, R is a member selected fromthe group consisting of hydrogen and methyl, R, is a fatty alcoholmoiety having from 10 to 22 carbon atoms, and n is an integer from to10. l

7. The composition of claim 1 wherein said activator for active oxytenis a member selected from the group consisting of tetraacetylglycoluril,tetrapropionyl- TCH=(IIHOTR= Q Q Q a CH=CH-, CH=CH and glycoluril,methyltriacetylglycoluril and diacetyldiben- X represents a membel'Selected from the group zoylglycoluriL sisting of -NH-, S, and -O, R,represents a 8. A process for the stabilization of opticalbrightenmember Selected from the group consisting of y ers againstdeterioration in aqueous solutions in the g lkyl having 1 t0 5 Carbonoms and phenyl, R. presence of copper ions and H,0, which consistsessenand R, represent members selected from the group consisting ofphenyl and phenyl substituted with at least taining (1) small amounts ofcopper ions, (2) an effec-' one substituent selected from the groupconsisting of tive amount for optical brightening for textiles of anopalkyl having 1 to 4 carbon atoms, hydroxyalkyl having tical brightenerhaving a formula selected from the 2 to 5 carbon atoms, alkoxy having 1to 5 carbon group consisting of atoms, chloro, CN, COOH, SO l-l, CO,Cland SO,N

and

CH=CH CH=CH W+.m A

wherein azolyl represents an azole structure of the for- R,,R,, and Rand R, are members selected from the mula selected from the groupconsisting of group consisting of hydrogen, alkyl having 1 to 5 carbonatoms, hydroxyalkyl having 2 to 4 carbon atoms and, taken together withthe nitrogen, piperidino, piperazino, morpholino and pyrrolidino, andtheir water- N N N soluble salts, and (3) an effective amount forbleaching A of a water-soluble inorganic percompound yielding N and H O,in aqueous solution, an amount of an activator for R said inorganicpercompounds selected from the group N N consisting of N-acyl and O-acylcompounds having 2 to 7' i r v M 9 carbon atoms in the acyl saidactivator having an ac- A re resents a m m cted from the rou conp 6 betsele g p tivatmg action of at least 3 In the Per-Acid Formation sistingof hydrogen and SOSH R represents a member test said percompound andsaid activator having presselected from the group consisting of hydrogenand ent in such ratio that from 0.01 to 4 mols of said activaalkylhaving 1 to 5 carbon atoms, R represents a memtor are present for eachgram-atom of active oxygen in ber selected from the group consrstmgofhydrogen and said inorganic percompound.

halogen, R, represents a member selected from the group consisting ofCN, SO l-l and SO,NHR, R, a: a i a: s

2. The composition of claim 1 containing from 99.98 to 97.5 percent byweight of component (a) mixture and 0.02 to 2.5 percent by weight ofcomponent (b) optical brightener.
 3. The composition of claim 2 whereinsaid activator for active oxygen has an activating action of at least4.5 in the Per-Acid Formation Test and said percompound and saidactivator are present in such a ratio thAt from 0.05 to 2 mols of saidactivator are present for each gram-atom of active oxygen in saidpercompound.
 4. The composition of claim 3 wherein said percompoundyielding H2O2 in aqueous solution is a water - soluble perborate.
 5. Thecomposition of claim 1 having an addition content, based on said totalcomposition, of at least one compound selected (1) from 0 to 5 percentby weight of a corrosion inhibitor selected from the group consisting oftriazoles and tetrazoles containing at least one of the groups Nme andNOMe where Me represents a metal or a hydrogen atom replaceable by ametal, (2) from 0 to 20% by weight of water-soluble salts of partialesters of fatty alcohols having 10 to 22 carbon atoms and theirethoxylated and propoxylated compounds having 1 to 10 alkoxyl groups,with orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid,and (3) from 0 to 10 percent by weight of an organic sequesteringbuilder salt for heavy metals.
 6. The composition of claim 5 whereinsaid water-soluble salts of partial esters has the formula
 7. Thecomposition of claim 1 wherein said activator for active oxyten is amember selected from the group consisting of tetraacetylglycoluril,tetrapropionylglycoluril, methyltriacetylglycoluril anddiacetyldibenzoylglycoluril.
 8. A process for the stabilization ofoptical brighteners against deterioration in aqueous solutions in thepresence of copper ions and H2O2 which consists essentially of the stepsof adding to an aqueous solution containing (1) small amounts of copperions, (2) an effective amount for optical brightening for textiles of anoptical brightener having a formula selected from the group consistingof